Apparatus and method for sulphonating fatty compounds



Sept. 13, 1938. D. s. WHITEMAN APPARATUS AND METHOD FOR SULHONATING FATTY COMPOUNDS 2 Sheets-Sheet 1 Filed Jan. 50, 1935 llll mm A 1v mm w R. wv

Sept. 13, 1938. D. s. WHITEMAN APPARATUS AND METHOD FOR SULPHONATING FATTY COMPOUNDS Filed Jari. so, 1935 2 sheets-sheet 2 www: Y, y

/y/ Mez/ ,sa /z//m M s. M 4 /d www@ Patented Sept. 13, 1938 UNITED STATES APPARATUS AND METHOD FOR SULPHO- NATING FATTY COMPOUNDS Daniel S. Whiteman, Philadelphia, Pa., assignor to Reilly-Whiteman-Walton Company, Con shohockcn, Pa., a corporation of Pennsylvania Application January 30, 1935, Serial No. 4,055

' 20 Claims.

My invention relates to methods and apparatus for sulphonating fatty compounds, such for example as glyceryl esters of fatty acids or fatty acids.

A purpose of my invention is to treat any quantity of fatty compound, large or small, with sulphuric acid or another suitable sulphonating agent as a continuous process accompanied by mechanical mixing, without burning or discoloring the fatty compound and without extensive hydrolysis in the case of a fatty oil.

A further purpose is to produce sulphonated fatty oils of comparatively low free 'fatty acid content.

A further purpose is to subject the sulphonating temperature of fatty oils to more accurate control and at the same time to make the temperature of fatty oil sulphonation less critical.

'A further purpose is to permit the operation 'upon fatty compounds at higher sulphonating temperatures without harmfully alfecting the resulting product.

A further purpose is to maintain continuous control at all times of the proportions of fatty compound and sulphonating agent fed to a sulphonation mixing vessel.

A further purpose is to continuously mechanically mix a fatty compound and sulphuric acid or another sulphonating agent quickly and intimately, to cool the reacting ingredients rapidly by removing them from thezone of initial mixing and holding them at reduced temperature for a suicient time to complete the reaction, to mix the reaction products quickly and intimately with a neutralizing and washing agent, to complete the neutralizing reaction and to centrifugally separate the sulphonated fatty compound from the neutralization and washing products.

A further purpose is to pass-a fatty compound and sulphuric acid or another sulphonating agent through a mixing mill containing a relatively thin envelope of liquid, sol that a thin lfilm of'fatty compound and sulphuric acid are mixed and cooling of the mixture is facilitated by the thinness of the envelope and the nearness of metallic cooling surfaces'to all parts of the mixture.

A further purpose is to subject a mixture of a fatty compound and a sulphonating agent to a. slow mixing action in a sulphonation completion vessel after initially relatively violently intermixing the fatty compound and sulphonating agent.

A further purpose is-automatically to proportion the neutralizing or washing agent to the excess sulphonating agent in continuous apparatus for sulphonating fatty compounds.

Further purposes appear inthe specification and in the claims.

The present application relates both to the methods involved and to the apparatus used.

In the drawings I have shown one main embodiment of the invention, with a modification, choosing the main embodiment and modification from the standpoints of convenience in illustration of the principles involved, satisfactory operation and simplicity.

All of the drawings are schematic, and are intended to avoid details which any person skilled in the art can readily supply.

Figure 1 is a diagrammatic view of a typical apparatus constructed in accordance with my invention.

Figure 1u is a fragmentary diagrammatic viev of a modification of Figure 1.

Fi'gure 2 is an enlarged central vertical section of one of the mixing mills shown in Figures 1 or `la.

. Figure 3 is an enlarged section of Figure 2 on theline 3-3 thereof.

Figurel: is an enlarged central vertical section of sulphonation completion vessel shown in Figures 1 and 1a. l.

In the drawings like numerals refer to like parts.

My invention relates to the sulphonation of fatty compounds. The sulphonating agent may be, for example, concentrated sulphuric acid, oleum, fuming sulphuric acid, sulphur trioxide vapor. Various fatty compounds may be treated. For example, fatty acids such as oleic acid may be sulphonated in accordance with my invention. Fatty oils, such as castor, oilve, rapeseed, teaseed and neatsfoot, may also be treated in accordance with my invention. These fatty oils are glyceryl esters of unsaturated fatty acids, but 1 am not restricted to glyceryl esters, but may sulphonate esters of fatty acids with mono, dior polyhydric alcohols, for example glycol esters.

sulphonation of fatty compounds, such as animal or vegetable oils, is commonly resorted to to change the properties of the oils, as to change the viscosity or surface tension, or to render the oils soluble in water. For example, castor oil is sulphonated to form turkey red oil, primarily to render the oil soluble. i

When a fatty oil, for example glyceryl trioleate or olein, istreated with concentrated sulphuric acid, a. series of complicated reactions takes place, depending upon the temperature, concentrations, etc. At low temperatures the primary reaction appears to be the addition of Sulphuric acid at points of unsaturation.

Olein H S 04H ciaooo(camcncmcnmom results at higher temperatures, for example above C. This reaction takes place to some extent at lower temperatures, or sulphated olein gradually changes to the sulphonic acid.

Simultaneously with the sulphonation, some of the fatty oil is hydrolyzed or partially hydrolyzed. For example, if one molecule of olein were hydrolyzed by one molecule of water, the result would be CHaOH neutralized, the lower the free 'fatty acid content. Hydrolysis of the reaction products to form free fatty acid continues as long as the reaction mixture is in the acid condition. One of the important advantages of this invention is to shorten the total time required for sulphonating glyceride oils, from the initial mixture of the oil and sulphonating agent to the final yseparation and nishing, and particularly from the neutralization or washing to the nal separation and finishing.

Sulphuric acid also tends to dehydrate and oxidize the glycerides and the albuminous matter present in the oil. This is known in the trade as charring" or burning," and is accompanied by the development of an undesirable dark color and by the odor of sulphur dioxide which is produced when Sulphuric acid is reduced by the material oxidized by the acid. Temperature is undoubtedly a factor in charring of the oil.

Hydrolysis and charring of the fatty oil are both favored by the presence of unmixed masses of Sulphuric acid, which is thus present at a given point in excessive concentrations, and by unduly high localized temperatures. Mere thorough mixing of the fatty oil and Sulphuric acid, without more,J does not solve the problem, because, while it breaks up the masses of Sulphuric acid and homogenizes the mixture, it does not take care of the heat developed when the fatty oil and sulphuric acid react. The fatty oils have quite low heat conductivities, and, while the heat conductivity of Sulphuric acid is higher than that of the fatty oils, it is still relatively low. The heat conductivity of the reaction mixture is of the same order of magnitude as those of the reacting components.

This explains the reason for the'diiculty encmooC(CH,)1CH=CH(CH,)1CH

Glyeeryl dioleate The presence of sulphonic acids catalyzes the hydrolysis (i. e., Twitchell reagents) and the result is that, unless precautions are taken, the content of free fatty acid may build up to an undesirable extent during sulphonation.

The matter is complicated by the fact that the products of the hydrolysis may react with sulphuric acid. Thus glyceryl dioleate mayform a mixed ester which may in turn be sulphonated at one of the double bonds. And the oleic acid may react with Sulphuric acid at the double bond in one of the manners referred to above, to form either sulphated oleic acid or oleic sulphonic acid. Sulphated oleic acid may be hydrolyzed to replace the (SOiH) group by an (OH) group. The sulphonic acid already contains an (OH) group. Either hydrolyzed sulphated oleic acid or the sulphonic acid may condense, with molecular rearrangement, with the (COOH) or acid group to form a lactone. Thus it is'seen that the consequences of hydrolysis are disastrous from the standpoint of obtaining a pure sulphonated glyceride.

From the standpoint of obtaining finished sulphonated glyceride oils of low free fatty acid con- Oleic acid tent, the time consumed in the processes is a vital 4 factor, and, in general, the more quickly the sul- 'phoriation is completed and the Sulphonated oil is countered when fatty compounds are sulphonated in a conventional apparatus in which Sulphuric acid is dropped slowly into a stirred and cooled mass of oil containedwithin a vat or kettle. Even though the stirring may be vigorous enough and the introduction ofthe sulphonating agent slow enough to prevent large masses of unreacted sulphuric acid from becoming localized, the develop- .ment of localized temperature rises, with consequent hydrolysis and charring, is diflicult to prevent. And of course, slow application of acid increases the cost.

Even when continuous streams of the fatty compound and Sulphuric acid fiow together in the presence of a blast of air, as in Dutch Patent No. 27,274, issued July 15, 1932, and the mixture is ledthrough a cooling coil, the danger of hydrolysis and charring because of incomplete mixing and localized temperature elevations is not material such as metal, `by mixing the sulphonating agent with the film on the cooling surface, and causing continuous motion of Ithe film t0 homogenize the mixture. The film is preferably moved by a'rotor. l Du'e to the thinness ofthe film, the distance of heat travel through the reaction mixture to the cooling surface is very small, and serious localized elevations in temperature are not possible.

'I'he motion of the rotor tends to cause the fatty compound and sulphuric acid to unite into a homogeneous film. The high velocities attained 4favor homogenization.

After the initial mixing, the reaction mixture is carried by me to a reaction completion vessel, where the sulphonation is completed while the mixture is being slowly stirred and cooled. 'Ihe complete sulphonation requires some time, and instantaneous contact between the fatty compound andthe sulphuric acid is not` enough. After the eflicient mixing which takes place in the sulphonation mixing milll and the end of the primary reaction, the dangers due to high temperature are Vno longer serious.Y

I next spread the mixture of the fatty compound and excess sulphonating agent in a film upon a cooling surface and introduce an aqueous neutralizing or washing solution into contact with the film of fatty compound and excess sulphonating agent. The lm is turbulently mixed and, due to the thinness of the film, the heat developed in the neutralization or washing is readilycarried to the cooling surface.

I preferably further mix the reaction products and neutralizing or washing solution to insure removal of the excess sulphuric acid, and then centrifugally separate the sulphonated fatty compound and the neutralization products or washing solution.

Careful tests with my novel method of sulphonation of fatty compounds have shown that I can produce continuously a lighter colored or less charred product than that of the prior art, and can safely allowthe sulphonating temperature to rise to higher values than those at which prior Aart sulphonators have been successfully operated.

In normal sulphonating operations upon fatty oils, the oil is charred if the temperature rises above about 35 C., but I have obtained extremely light colored sulphonated fatty oils when the temperature rose to as highas about 66 C. This is, of course, an exceptionally high temperature and the sulphonation will desirably be carried out at lower temperature. One explanation of the fact thatcharring does not occur at temperatures as high as 66 C is that localizedtemperature elevations present in prior art sulphonators, but never accurately measured in them, are avoided in my sulphonator. Another explanation is that cooling is very rapid in my sulphonator, so that the fatty oil is subject to the high temperature for a very short time.

Thus by my process the fatty oil is' never subjected simultaneously to any appreciable localized excess of free sulphonating agent'and high temperature.

I also nd that I can produce sulphonated fatty oils of lower free fatty acid content than the commercial methods of the prior art. This I attribute partly to the decreased hydrolysis during sulphonation, and partly to the continuous and relatively rapid separation of the sulphonated oil from the neutralization products or washing solution. I have observed that, if a vmixture of sulphonated oil, excess sulphuric acid and salt solution be allowed to stand indefinitely, for example over night for settling purposes, the content of free fatty acid increases markedly. For example. I have found that the free fatty acid of the nishedoil, increased in one instance after standing over nlghi: in contact with salt solution, from in the evening to 18% the next morning. My centrifuge separation avoids this difiiculty by virtue of the rapidity of its action.,

Where I refer throughout the specification and claims to neutraliaztion, I mean to include partial neutralization. In fact, in the art neutralization Onen of the factors which, according to my ex- .periments, assists in obtaining sulphonated fatty compounds of low free fatty acid content is the shortness of the elapsed time from the neutralization (or washing) of the sulphonation reaction mixture to the separation of the sulphonated fatty compound from the neutralizing (or washing) liquid. It will benoted that, in the conventional practice and in the processes according to my invention, the neutralized (or washed) reaction mixture is still slightly acid and is considerably diluted-and therefore much more susceptible to lhydrolysis than the more concentrated acidic reaction mixture.

I have observed that. where the neutralized reaction mixture is allowed to stand for. an extended length of time before separation from the neutralizing (or washing) liquid, or where a separating process such as settling is used which entails extended delay, considerable increase in the free fatty acid content results and the free fatty acid content may even double in an ordinary case.

To avoid this diiilculty I find that very rapid separation of the neutralizing (or washing) liquid from the sulphonated fatty compound is desirable and that the neutralizedfor washed) reaction mixture should pass to the separating mechanism almost immediately after neutralization. Where the elapsed time from neutralization (or washing) to separation is less than minutes, the increase in free fatty acid is very slight, and good results are obtained even when the elapsed time is as great as 30 minutes. vLonger times produce marked increase in free fatty acid content.

I may by my method sulphonate any quantity of fatty compound, from a few gallons up. The proportions of fatty compound and sulphonating agent are under full control at all times.

The sulphonator of my invention is'not to be confused with devices intended to refine petroleum by treating it with sulphuric acid to remove unsaturated compounds, sulphur compounds and other impurities as a sludge. The reaction here is instantaneous, and merely involves direct addition to the unsaturated compounds at the double bond. As the bulk of the petroleum `consists of saturated compounds which are inert to sulphuric acid even at rather high temperatures, the need for accurate temperature even be accomplished without neutralizing or y washing.

' bearings, not shown.

In the drawings I illustrate a typical fatty compound sulphonator constructed in accordance with my invention. The fatty oil, fatty acid, etc. which is to undergo treatment in contained within a tank 20 cooled by a cooling coil 2l having suitable inlet and outlet connections 22 and 23 to a source of cooling medium such as brine or cold Water. The fatty compound leaves the tank 20 through`a pipe 2t to a fatty compound feed pump 25 which may be a centrifugal pump.

As later explained, all of the pumps used in `:my apparatus may desirably have a common drive, so that the rate of production of sulphonated fatty compounds may readily be controlled. I illustrate an electric motor 26 driving a cone pulley 2l, which in turn drives a cooperating cone pulley 2B through a belt 29, suitably guided by means not shown. The cone pulley 25 is on a common drive shaft 3il,which rotates in suitable By varying the position of the belt 29 on the cooperating cone pulleys 2l and 2t, any suitable speed of rotation of the common drive shaft 3@ may be obtained.

The common drive shaft 50 carries suitable sprockets 3 l, 32 and 33, the latter of which drives the sprocket till on the fatty compound feed pump 25 by a chain 35.

From the fatty compound feed pump 25, the fatty compound passes by the pipe 35 to the sulphonation mixing mill 35. A suitable sulphonating agent, for example concentrated sulphuric acid, is held in a corrosion resistant tanlr. 5l. It will be understood that all parts of my apparatus which come in contact with corrosive chemicals are made of suitable corrosion resisting material, such as stainless steel or lVIonel metal. From the tank 3l, the sulphonating agent is withdrawn though a pipe 35 by a sulphonating agent feed pump 39 which passes measured quantities of sulphonating agent to the sulphonation mixing mill through a pipe lu.

The sulphonating agent feed pump 35 is driven by a chain All from the common drive shaft sprocket 32 to a sprocket t2 of a variable speed transmission t3, which in turn drives the sulphonating agent feed pump 39 by a sprocket Mi, through a chain :i5 to a sprocket i6 on the pump. The speed of the sulphonating agent feed pump 39 with respect to the c ommon drive shaft Si@ may be varied infinitely within any chosen range by the speed change lever @l in well known manner.

It will be evident that the fatty compound and the sulphonating agent are supplied to the sulphonation mixing mill under pressure from' the respective pumps.

The sulphonation mixingmill 35 is shown more in detail in Figures 2 and 3. In the form shown its axis is vertical, to avoid the necessity of having a tight packing between the mill and the motor at the top, but, subject to the need of proper packings, the axis of the mill may be in any direction. The mill comprises a preferably stationary cooling surface which in this case is outside and a moving surface, in close proximity, which in this case is inside. The cooling surface i8 is a tubular metallic casing which is maintained at a low temperature by a cooling jacket 59, through whose hollow interior 50 a cooling medium, suitably brine or cold water, flows from an inlet 5l to an outlet 52.

Within the annular cooling surface a rotor 53, rotatably supported on a bottom bearing 5t secured to the base of the mill, is driven at high speed by a motor 5t. The fatty compound enters the clearance space 5l between the cooling surface t8 and the rotor 53-at the bottom through the pipe 35, and courses upwardly. The sulphonating agent enters through the pipe l0 slightly above the fatty compound inlet, thus protecting the bearing 56 somewhat from the sulphonating agent, and insuring it perfect lubrication from the fatty compound.

The rotor 53 is preferably of uniform cylindrical cross section for a substantial part of its axial length. It is of importance in my invention to have the clearance space 5l so small that the fatty compound and sulphonating agent spread out in a thin lm against the cooling surface. Experiment indicates that the distance from the surface of the rotor 53 to the cooling surface 3 8 should be less than one-quarter of an inch and that best results are obtained with a distance of less than one-eighth of an inch. I have found a clearance of about one-tenth of an inch to be very desirable.

During the axial travel of the fatty compound and sulphonating agent in the mill, the lms of fatty compound and sulphonating agent are turbulently mixed and the heat developed during the reaction is extracted by the cooling surface. To obtain rapid and intimate mixing the rotor is preferably operated at high peripheral speed, desirably in excess of 500 feet per minute. The peripheral speed is of course .a function of the speed of rotation and of the rotor diameter. While I am not prepared to explain in full detail the reasons for the' very efficient turbulent mixing obtained in the sulphonation mixing mill, I believe turbulent mixing is the hydraulic shear between lms respectively adhering to the stationary cool ing surface and to the rotor. One effect of the turbulent mixing is to cause the reactants to disperse in a molecularsense and another effect is constantly to re-orient the reactant molecules with respect to each other and thus greatly increase the probability of molecule to molecule contact while the molecules are oriented in that Position most favorable for chemical interaction. When the mixture of partially sulphonated fatty compound and excess sulphonating agent reaches the top of the sulphonation mixing mill, it is received in the space 58, thrown centrifugal- 1y to the outside, and discharged through a pipe 59 to a reaction completion vessel, as shown in Figure 1, or, by modification of the apparatus, discharged through a pipe lill to another sulphonation mixing mill as shown in Figure 1a. The shaft 53 is reduced in diameter at the top at Sil, and the reduced shaft is surrounded by a cap Gi, which prevents any travel of the reaction mixture up the shaft and into the motor 56.

The reaction completion vessel 62 is shown in detail .in Figure 4. In the case of sulphonating fatty` compounds, the reaction is not instantaneous, Yalthough it is by no means so slow as prior art .intermittent methods would indicate.

lI do not intend to indicate that the size of the -will be substantially complete when the reacf tion mixture leaves the reaction completion vessel. After the mixing of the fatty compound and sulphonating agent has taken place in one or more sulphonation mixing mills, the reaction mixture enters the hopper 63 of the reaction completion vessel through the pipe 59, and, while in the reaction completion vessel, is stirred at relatively low speed by the stirrer 64 on the shaft 65, journalled at the base 66 in a bearing 61. 'Ihe shaft 65 is driven by the motor 68 through speed reduction gearing 69, of well known character.

The wall 10 of the reaction completion vessel is surrounded by a cooling jacket 1|, having inlet 'and outlet at 12 and 13 for a cooling medium, such asbrine or cold water.

'Ihe rate of withdrawal of reaction mixture from the reaction completion 'vessel 62 through the pipe 14 is controlled by the reaction mixture pump 15, which discharges a volume roughly equal to the total volume of fatty compound and liquid sulphonatlng agent added te the sulphonation mixing mill. The reaction mixture pump 15 is driven from common shaft sprocket 3| by -a chain 16 to a sprocket 11 of the variable speed transmission 18, equipped with the speed change lever 19 which permits infinite speed variation within the chosen range. The variable speed transmission 18 drives two sprockets 80 and 8| at the same speed and preferably on the same shaft, and the latter sprocket drives the reaction mixture pump 15 by a chain 82 to the pump sprocket 08. t

From the reaction mixture pump 15, the mixture of sulphonated fatty compound and excess sulphonating agent passes to a neutralizing mill 84 through a pipe 8 5 which isdesirably surrounded for part of its length by a cooling jacket 86 which receives a cooling medium through an inlet 81 and discharges it through an outlet 88. If desired, the cooling jacket 86 may be omitted, as shown in Figure 1a. The neutralizing mill 84 receives a neutralizing agent, for example sodium hydroxide solution, from a tank 89 through a pipe 90, a neutralizing agent pump 9| and a pipe 92. The neutralizing agent pump 9| is driven from sprocket 80 of .variable speed transmission 18 through chain 98 to sprocket 94 of variable Speed transmission 95, which in turn drives pump sprocket 96 by chain 91 from sprocket 98. Speed change lever 99 permits innite change in the speed of neutralizing agent pump 9| with respect to common drive shaft 30 within the chosen range. The speed of neutralizing agent pump 9| i's9 of course also affected by speed change lever 'I'he neutralizing mill 84 may be desirably exactly like the sulphonation mixing mill 30 already described. The same' advantages of thorough mixing and eiilcient heat removal already described in the case of the sulphonation mixing mill are also true of the neutralizing mill. The lm of sulphonated fatty compound and excess sulphonatlng agent is mixed with the neutralizing agent, and the heat of the reaction is extracted, in the neutralizing mill.

If desired, the neutralizing mill 84 may be used purely as a washing mill, in which case the tank 89 will desirably contain sodium chloride or other salt solution. The use of the mill 84 for neutraliz` ing is the preferable use, however, so that elsewhere I refer generally to the neutralizing use, although where I refer to neutralizing I mean to include, the introduction of aqueous solutions generally, for example for washing. As already noted, neutralization is not really complete until nishing. if then.

The effluent from the neutralizing mill 84 passes by a pipe to a mixing trough |0|, where a stlrrer |02 driven by a motor |03 equalizes any slight momentary inequalities in distribution of the neutralizing agent, and also allows time for some slight localization of globules of the respective phases in the emulsion.

From the mixing trough |0| the emulsion ows by gravity through 'a pipe |04 to a centrifugal separator |05, preferably entering the bottom of the separator. 'Ihe heavy sodium sulphate solution is separated from the lighter sulphonated fatty compound in the centrifugal separator, the washing liquid passing by the pipe |06 from the centrifugal separator to the sump |01, and the sulphonated fatty compound flowing by the pipe |08 to the tank |09, in which suitable nishing may be carried out, preferably at once.

While I prefer to use a liquid sulphonatlng agent, a gaseous sulphonatlng agent may be supplied if desired. Figure 1a is similar to Figure l except in certain features., mentioned below. Fatty compound supplied as explained in connection with Figure 1 passes through a plurality ot sulphonation mixing mills 36' and 362 connected by a pipe l0. Gaseous sulphur trioxide' from a suitable source conventionally illustrated at is fed to the respective sulphonation mixing mills through pipes 00' and 402 having valves H2 and H3 to control the proportional feed to each sulphonation mixing mill.

The through-put of the sulphonator may be controlled by'the speed of common drive shaft 30. In experimental work I have found a throughput of one gallon of fatty compound per minute' to be entirely satisfactory for continuous operation, with a clearance of about 0.1 inch and a rotor i diameter of about 1.5 inches.`

'I'he proportion of sulphonatlng agent to fatty compound may be varied by shifting the speed change lever'41 of the variable speed transmission 43 in Figure l. The extent of neutralization may be controlled in Figure 1 by shifting the change speed lever 98 of the variable speed transmission 95. This is conveniently done by taking samples at the sample tap ||4, and adjusting the neutralization until the samples 'show neutrality to congo red paper, or a pH of about 4.

. If desired, the neutralization or washing may be automatically controlled by any suitable automatic hydrogen ion control mechanism, the detail of which is no part of my invention. For example, I may use an antimony electrode cell hydrogen ion controller of the type now generally 'available onthe market. In Figure la I show an antimony cell ||5 continuously measuring the hydrogen ion concentration in the mixing trough |0| and continuously regulating the feed of neutralizing or washing agent bythe controller ||6, connected electrically at ||1 with the antimony cell and changing the speed of the variable speed transmission 95 to vary the feed of neutralizing or washing agent.

While I generally prefer to introduce the A smaller volume of liquid into a moving lm of the larger volume of liquid, that is, to introduce the sulphonatlng agent into a moving film of the fatty compound or the neutralizing (or washing) liquid into a moving lm of the reaction mixture, the procedure may to somewhat less advantage be reversed, introducing the fatty compound into a moving lm of the sulphonatlng agent or introducing the reaction mixture into a moving lm *of neutralizing (or washing) solution.

It will be evident that other forms of control may be supplied by persons skilled in the art.

In view of my invention and disclosure variations and modifications to meet individual whim 91' particular need will doubtless become evident to others skilled in the art, to obtain all or part of the benefits of my invention without copying the structure shown, and I, therefore, claim all such in so far as they fall within the reasonable spirit and scope of the following claims.

Having thus described my invention, what I claim as new and desire to secure by Letters Patent is:-

1. rIi'he method of sulphonating a fatty compound, which comprises continuously progressing the fatty compound as a film between relatively moving adjacent surfaces and introducing a sulphonating agent into the continuously moving film of fatty'compound.

2. The method of sulphonating a fatty compound, which comprises continuously progressing the fatty compound as a film of less than onequarter of an inch thickness between relatively moving adjacent surfaces and introducing a sulphonating agent into the continuously moving lm of fatty compound.

3. The method of sulphonating a fatty compound, which comprises continuously progressing the fatty compound as a lm between adjacent surfaces, relatively moving the surfaces, cooling one of the surfaces and adding a sulphonating agent to the continuously moving film v of fatty compound.

4. The method of of sulphonating a fatty compound, which comprises continuously progressing the fatty compound as a filmof less than onequarter of an inch thickness, between relatively moving adjacent metallic surfaces, adding a sul phonating agent to the continuously moving film of fatty compound and withdrawing the heat developed through one of the metallic surfaces, whereby the thinness of the film facilitates withdrawal of the heat and assists in avoiding charrng of the fatty compound.

5. The method of sulphonating a fatty compound, which comprises continuously progressing the fatty compound as a iilrn, adding a sulphonating agent to the continuously moving film of fatty compound, shearing the film between relatively moving walls separated not more than one-quarter of an inch and concurrently with-v drawing the heat formed, whereby the thickness of the film facilitates withdrawal of the heat and assists in avoiding charring of the fatty compound.

6. The method of sulphonating a fatty oil, which comprises continuously progressing the fatty oil as a whirling nlm, adding sulphuric acid to the whirling film of fatty oil,u shearing the film between relatively rotating metallic surfaces and withdrawing heat through one of the metallic surfaces, whereby a sulphonated oil of reduced free fatty acid content is produced.

7. The method of neutralizing the excess sulphonating agent in. a reaction mixture resulting from the sulphonation of a fatty compound, which comprises continuously progressing the reaction mixture as a film between relatively moving adjacent surfaces, introducing a neutralizing agent into the film, shearing, the neutralizing agent and reaction mixture between the surfaces and concurrently withdrawing the heat formed from the mixed film through one of the surfaces.'

8. The method of sulphonating a fatty compound, which comprises continuously progressing proportioned quantities of the fatty compound and a sulphonating agent as a mixed film between relatively moving adjacent surfaces, one of which is a rst cooling surface, withdrawing heat formed through the first cooling surface, slowly mixing thel fatty compound and sulphonating agentl to complete the reaction, continuously progressing proportioned quantities of the reaction mixture'and a neutralizing agent as a mixed film between relatively moving adjacent surfaces, one of which is a second cooling surface, withdrawing heat formed through the second cooling surface, homogenizing the mixture and centrifugally separating the sulphonated fatty compound from the remainder of the mixture.

9. The method of sulphonating a fatty compound, which comprises continuously mixing a fatty compound and a proportioned quantity of a sulphonating agent as a film between relatively moving adjacent surfaces, the thickness of the mixed film not exceeding onequarter of an inch, ncurrently withdrawing heat formed, continuously stirring the mixture for reaction completion, continuously mixing the stirred reaction mixture and a proportioned quantity of a neutralizing agent as a film between relatively moving adjacent surfaces, the thickness of the mixed film not exceeding one-quarter of an inch, and concurrently withdrawing heat formed.

l0. The method of sulphonating a fatty compound, which comprises continuously mixing a fatty compou'nd and a proportioned quantity of a sulphonating agent as a film between relatively moving adjacent surfaces, the thickness of the mixed film not exceeding one-quarter of an inch, concurrently withdrawing heat formed, continuously stirring the mixture for reaction completion, continuously mixing the stirred reaction mixture and a proportioned quantity of a neutralizing agent as a film between relatively moving adjacent surfaces, the thickness of the mixed film not exceeding one-quarter of an inch, concurrently withdrawing heat formed, and continuously centrifugally separating the sulphonn ated fatty compound from the remainder of the mixture.

11. In a sulphonator for fatty compounds, relatively rotatable cooperating members having a clearance space of. film thinness between them through which the fatty compound and sulphonating agent may ow means for rotating one of the members, means for cooling one of the members, means for pumping a fatty compound, conduit means communicating from said means for pumping the fatty compound to the clearance space, meansl for pumping a sulphonating agent proportionally to the means for pumping the fatty compound and conduit means communicating from said means for pumping the sulphonating agent to the clearance space. l2. In a sulphonator for fatty compounds, a casing having an annular interior, means for cooling the casing, a rotor within and cooperating with the casing having a slight clearance fromthe casing for a substantial axial length, a plurality of inlet conduits adjacent one endv of the rotor and communicating with the clearance space, an outlet conduit adjacent the opposite end of the rotor and means for driving the rotor.

13. A tubular mixing mill for the sulphonation of fatty compounds comprising a tubular casing, means for cooling the casing, a rotor of substantially uniform cross section for a substantial axialdistance within and cooperating with the casing, having a clearance from the casing of less than one-quarter inch, means for turning the rotor, an inlet to the clearance space adjacent one end of the rotor and an outlet from the clearance space adjacent the other end.

14. A mixing mili for use in the sulphonation of fatty compounds comprising cooperating relatively rotatable circular members having a clear- `ance of less than one-quarter of an inch for a substantial axial distance, means for rotating one of the members, means for cooling one of the members, means for introducing the reaction ingredients adjacent one end and passing them through the mill and means for withdrawing the reaction mixture adjacent the other end of the mill.

15. A mixing mill for use in the sulphonation of fatty compounds comprising a tubular vertical casing, cooling means for the casing, a cylindrical vertical rotor within and cooperating with the casing, leaving a clearance'space between the casing and the rotor of less than one-quarter of an inch, inlet and outlet conduits to and from the clearance space adjacent the ends thereof, and means at the top of the rotor for driving the rotor at a peripheral speed in excess of 500 feet per minute.

16. A sulphonation mixing mill for fatty compounds comprising a tubular vertical casing, cooling means for the casing, a cylindrical vertical rotor within and cooperating with the casing, having a clearance from the casing of less than one-quarter of an inch for a substantial axial lengtn, a bearing for the rotor at the bottom, means for introducing -a fatty compound under pressure adjacent the bearing, means for introducing a sulphonating agent under pressure above the point of introduction of the fatty compound, means for withdrawing the reaction mixture adjacent the top of the rotor and means for1 driving the rotor at the top, whereby the fatty compound under treatment serves to lubricate the bearing.

17. In a sulphonator for fatty compounds, a sulphonation mixing millhaving a cooling surface and having a rotor providing a clearance space of not more than one-quarter inch between the surface and the rotor, in which space turbulent mixing takes place, means for continuously introducing a fatty compound to the space and means for continuously introducing sulphur trioxidey to the space.

18. In a device for sulphonating a fatty compound by a sulphonating agent, a mixing mill having an annular conduit of film thinness provided with angularly relatively movable nearly ing one wall with respect to the opposing nearly adjacent other wall and means for concurrently progressing streams of the fatty compound and of the sulphonating agent into the conduit at parts of the conduit toward one end thereof and for delivering the resulting stream of sulphonating compound out of the conduit from a part of the conduit toward the other end thereof,

19. In a device for sulphonating a fatty compound by a sulphonating agent, a mixing mill having an annular conduit of lm thinness provided With angularly relatively movable nearly adjacent inner and outer walls, means for angularly rotating one wall .with respect to the opposing nearly adjacent other wall, means for cooling one of the walls, and means for concurrently progressing streams of the fatty com- -poundi'and of the sulphonating agent into the conduit at parts of the conduit toward one end thereof and for delivering the resultant stream of sulphonated compound out of the conduit from a part of the conduit toward the other end thereof, the sulphonating agent being progressed into the conduit at a point longitudinal of the conduit between the part at which the fatty compound is introduced and the part at which the sulphonated stream is delivered, whereby the streamof sulphonating agent is delivered into a stream of fatty compound, as distinguished from delivering the stream of fatty compound into a stream of sulphonating agent.

20. In a device for sulphonating a fatty compound by a sulphonating agent, a mixing mill having an annular conduit of film thinness provided with angularly relatively movable nearly adjacent inner and outer walls, means for angularly rotating the inner Wall about its longitudinal axis, means for cooling one of the walls, a bearing for the inner wall near one end of the conduit and means for concurrently progressing streams of the fatty compound and of the sulphonating agent into the conduit at parts o1" the conduit toward the end having the bearing and for delivering the resulting stream of sulphonated compound out of the conduit from a part of the conduit toward the other end thereof, the fatty compound being progressed into the conduit at a part of the conduit located longitudinally of the conduit between the bearing and the said part into which the sulphonating agent is progressed, whereby the stream of fatty compound protects the bearing from the stream of sulphonating agent.

DANIEL S. WHITEMAN. 

